Diphenylamine salan catalyst

ABSTRACT

Catalysts comprising Salan ligands with bridged or unbridged diphenyl amine moieties. Also, catalyst systems comprising the catalyst and an activator; methods to prepare the ligands, catalysts and catalyst systems; processes to polymerize olefins using the catalysts and/or catalyst systems; and the olefin polymers prepared according to the processes.

FIELD OF THE INVENTION

This invention relates to novel catalyst compounds comprising Salanligands and catalyst systems comprising such and uses thereof.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hencethere is interest in finding new catalyst systems that increase thecommercial usefulness of the catalyst and allow the production ofpolymers having improved properties.

There is a need in the art for new and improved catalysts and catalystsystems to obtain new and improved polyolefins, polymerizationprocesses, and the like. Accordingly, there is a need in the art for newand improved catalyst systems for the polymerization of olefins for oneor more of the following purposes: to achieve one or more specificpolymer properties, such as high polymer melting point and/or highpolymer molecular weights; to increase conversion or comonomerincorporation; and/or to alter comonomer distribution withoutdeterioration of the properties of the resulting polymer. The instantdisclosure is directed to novel catalyst compounds, catalysts systemscomprising such compounds, and processes for the polymerization ofolefins using such compounds and systems in satisfaction of the need inthe art.

SUMMARY OF THE INVENTION

The instant disclosure is directed to catalyst compounds, catalystsystems comprising such compounds, processes for the preparation of thecatalyst compounds and systems, and processes for the polymerization ofolefins using such catalyst compounds and systems.

In an embodiment of the invention, the catalyst compound comprises Group3, 4, 5 and/or 6 dialkyl compounds supported by a heteroaryl-substitutedtetradentate di-anionic Salan ligand.

In an embodiment of the invention, a catalyst compound is represented bythe formula:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², N³ and N⁴ are nitrogen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical; and    -   each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen,        a C₁-C₄₀ hydrocarbyl radical, a functional group comprising        elements from Group 13-17 of the periodic table of the elements,        or two or more of R¹ to R³² may independently join together to        form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a        combination thereof.

In an embodiment of the invention, a catalyst compound is represented bythe formula:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², N³ and N⁴ are nitrogen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical; and    -   each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen,        a C₁-C₄₀ hydrocarbyl radical, a functional group comprising        elements from Group 13-17 of the periodic table of the elements,        or two or more of R¹ to R³² may independently join together to        form a C₄ to C₆₂ cyclic or polycyclic ring structure wherein        neither of R⁶ nor R²⁹ join together with R¹³ or R³⁰ to form        direct covalent bonds between the respective aromatic rings and        wherein neither of R²⁶ nor R³¹ join together with R¹⁹ or R³² to        form direct covalent bonds between the respective aromatic        rings, or a combination thereof.

In an embodiment of the invention, a catalyst system comprises anactivator and a catalyst compound represented by the formula:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², N³ and N⁴ are nitrogen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical; and    -   R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,        R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,        R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen, a        C₁-C₄₀ hydrocarbyl radical, a functional group comprising        elements from Group 13-17 of the periodic table of the elements,        or two or more of R¹ to R³² may independently join together to        form a C₄ to C₆₂ cyclic or polycyclic ring structure wherein        neither of R⁶ nor R²⁹ are directly bridged to R¹³ or R³⁰ and        wherein neither of R²⁶ nor R³¹ are directly bridged to R¹⁹ or        R³², or a combination thereof.

In an embodiment of the invention, a process to polymerize olefinscomprises contacting one or more olefins with a catalyst system at atemperature, a pressure, and for a period of time sufficient to producea polyolefin, the catalyst system comprising an activator and a catalystcompound represented by the formula:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², N³ and N⁴ are nitrogen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   Y is a divalent C₁ to C₂₀ hydrocarbyl; and    -   each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen,        a C₁-C₄₀ hydrocarbyl radical, a functional group comprising        elements from Group 13-17 of the periodic table of the elements,        or two or more of R¹ to R³² may independently join together to        form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a        combination thereof.

This invention also relates to catalyst systems comprising suchcompounds, processes for the preparation of the catalyst compounds andsystems, processes for the polymerization of olefins using such catalystcompounds and systems and the polyolefins obtained from such processes.

DETAILED DESCRIPTION

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as in Chem. Eng.News, 1985, 63, 27. Therefore, a “Group 4 metal” is an element fromGroup 4 of the Periodic Table.

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, an arrow indicates that the bond may bedative, and each dashed line represents a bond having varying degrees ofcovalency and a varying degree of coordination.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document unless otherwisespecified. For purposes of this disclosure, a hydrocarbyl radical isdefined to be C₁ to C₇₀ radicals, or C₁ to C₂₀ radicals, or C₁ to C₁₀radicals, or C₆ to C₇₀ radicals, or C₆ to C₂₀ radicals, or C₇ to C₂₀radicals that may be linear, branched, or cyclic where appropriate(aromatic or non-aromatic); and includes hydrocarbyl radicalssubstituted with other hydrocarbyl radicals and/or one or morefunctional groups comprising elements from Groups 13-17 of the periodictable of the elements. In addition two or more such hydrocarbyl radicalsmay together form a fused ring system, including partially or fullyhydrogenated fused ring systems, which may include heterocyclicradicals.

The term “substituted” means that a hydrogen atom and/or a carbon atomin the base structure has been replaced with a hydrocarbyl radical,and/or a functional group, and/or a heteroatom or a heteroatomcontaining group. Accordingly, the term hydrocarbyl radical includesheteroatom containing groups. For purposes herein, a heteroatom isdefined as any atom other than carbon and hydrogen. For example, methylcyclopentadiene (Cp) is a Cp group, which is the base structure,substituted with a methyl radical, which may also be referred to as amethyl functional group, ethyl alcohol is an ethyl group, which is thebase structure, substituted with an —OH functional group, and pyridineis a phenyl group having a carbon in the base structure of the benzenering substituted with a nitrogen atom.

For purposes herein, a hydrocarbyl radical may be independently selectedfrom substituted or unsubstituted methyl, ethyl, ethenyl and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl,tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl,pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl,nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl,eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl,pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, andtriacontynyl.

For purposes herein, hydrocarbyl radicals may also include isomers ofsaturated, partially unsaturated and aromatic cyclic structures whereinthe radical may additionally be subjected to the types of substitutionsdescribed above. The term “aryl”, “aryl radical”, and/or “aryl group”refers to aromatic cyclic structures, which may be substituted withhydrocarbyl radicals and/or functional groups as defined herein.Examples of aryl radicals include: acenaphthenyl, acenaphthylenyl,acridinyl, anthracenyl, benzanthracenyls, benzimidazolyl,benzisoxazolyl, benzofluoranthenyls, benzofuranyl, benzoperylenyls,benzopyrenyls, benzothiazolyl, benzothiophenyls, benzoxazolyl, benzyl,carbazolyl, carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl,cyclohexenyl, methylcyclohexyl, dibenzoanthracenyls, fluoranthenyl,fluorenyl, furanyl, imidazolyl, indazolyl, indenopyrenyls, indolyl,indolinyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isoxazolyl,methyl benzyl, methylphenyl, naphthyl, oxazolyl, phenanthrenyl, phenyl,purinyl, pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridinyl,pyrimidinyl, pyrrolyl, quinazolinyl, quinolonyl, quinoxalinyl,thiazolyl, thiophenyl, and the like.

It is to be understood that for purposes herein, when a radical islisted, it indicates that the base structure of the radical (the radicaltype) and all other radicals formed when that radical is subjected tothe substitutions defined above. Alkyl, alkenyl, and alkynyl radicalslisted include all isomers including where appropriate cyclic isomers,for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl,tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls);pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1-ethylpropyl, and nevopentyl (and analogous substitutedcyclobutyls and cyclopropyls); butenyl includes E and Z forms of1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl (andcyclobutenyls and cyclopropenyls). Cyclic compounds having substitutionsinclude all isomer forms, for example, methylphenyl would includeortho-methylphenyl, meta-methylphenyl and para-methylphenyl;dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and3,5-dimethylphenyl.

Likewise the terms “functional group”, “group” and “substituent” arealso used interchangeably throughout this document unless otherwisespecified. For purposes herein, a functional group includes both organicand inorganic radicals or moieties comprising elements from Groups 13,14, 15, 16, 17 of the periodic table of elements. Suitable functionalgroups may include hydrocarbyl radicals, e.g., alkyl radicals, alkeneradicals, aryl radicals, and/or halogen (Cl, Br, I, F), O, S, Se, Te,NR*_(x), OR*, SeR*, TeR*, PR*_(x), AsR*_(x), SbR*_(x), SR*, BR*_(x),SiR*_(x), GeR*_(x), SnR*_(x), PbR*_(x), and/or the like, wherein R is aC₁ to C₂₀ hydrocarbyl as defined above and wherein x is the appropriateinteger to provide an electron neutral moiety. Other examples offunctional groups include those typically referred to as amines, imides,amides, ethers, alcohols (hydroxides), sulfides, sulfates, phosphides,halides, phosphonates, alkoxides, esters, carboxylates, aldehydes, andthe like.

For purposes herein “direct bonds,” “direct covalent bonds” or “directlybridged” are used interchangeably to refer to covalent bonds directlybetween atoms that do not have any intervening atoms. Where reference ismade herein to two substituents joining together to form a cyclic orpolycyclic ring structure, one substituent is directly bridged toanother substituent when the two substituents together form only acovalent bond containing no atoms, i.e., the substituents are notdirectly bridged if they together comprise a bridge of at least oneatom.

For purposes herein an “olefin,” alternatively referred to as “alkene,”is a linear, branched, or cyclic compound comprising carbon and hydrogenhaving at least one double bond. For purposes of this specification andthe claims appended thereto, when a polymer or copolymer is referred toas comprising an olefin, the olefin present in such polymer or copolymeris the polymerized form of the olefin. For example, when a copolymer issaid to have an “ethylene” content of 35 wt % to 55 wt %, it isunderstood that the mer unit in the copolymer is derived from ethylenein the polymerization reaction and said derived units are present at 35wt % to 55 wt %, based upon the weight of the copolymer.

For purposes herein a “polymer” has two or more of the same or different“mer” units. A “homopolymer” is a polymer having mer units that are thesame. A “copolymer” is a polymer having two or more mer units that aredifferent from each other. A “terpolymer” is a polymer having three merunits that are different from each other. “Different” in reference tomer units indicates that the mer units differ from each other by atleast one atom or are different isomerically. Accordingly, thedefinition of copolymer, as used herein, includes terpolymers and thelike. An oligomer is typically a polymer having a low molecular weight,such as an Mn of less than 25,000 g/mol, or in an embodiment of theinvention less than 2,500 g/mol, or a low number of mer units, such as75 mer units or less. An “ethylene polymer” or “ethylene copolymer” is apolymer or copolymer comprising at least 50 mole % ethylene derivedunits, a “propylene polymer” or “propylene copolymer” is a polymer orcopolymer comprising at least 50 mole % propylene derived units, and soon.

For the purposes of this disclosure, the term “α-olefin” includes C₂-C₂₂olefins. Non-limiting examples of α-olefins include ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene,1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.Non-limiting examples of cyclic olefins and diolefins includecyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane.

The terms “catalyst”, “catalyst compound”, and “transition metalcompound” are defined to mean a compound capable of initiatingpolymerization catalysis under the appropriate conditions. In thedescription herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, or a transition metal compound, andthese terms are used interchangeably. A catalyst compound may be used byitself to initiate catalysis or may be used in combination with anactivator to initiate catalysis. When the catalyst compound is combinedwith an activator to initiate catalysis, the catalyst compound is oftenreferred to as a pre-catalyst or catalyst precursor. A “catalyst system”is combination of at least one catalyst compound, at least oneactivator, an optional co-activator, and an optional support material,where the system can polymerize monomers to polymer. For the purposes ofthis invention and the claims thereto, when catalyst systems aredescribed as comprising neutral stable forms of the components it iswell understood by one of ordinary skill in the art that the ionic formof the component is the form that reacts with the monomers to producepolymers.

For purposes herein the term “catalyst productivity” is a measure of howmany grams of polymer (P) are produced using a polymerization catalystcomprising W grams of catalyst (cat), over a period of time of T hours;and may be expressed by the following formula: P/(T×W) and expressed inunits of gPgcat⁻¹hr⁻¹. Conversion is the amount of monomer that isconverted to polymer product, and is reported as mol % and is calculatedbased on the polymer yield and the amount of monomer fed into thereactor. Catalyst activity is a measure of how active the catalyst isand is reported as the mass of product polymer (P) produced per mole ofcatalyst (cat) used (kg P/mol cat).

An “anionic ligand” is a negatively charged ligand which donates one ormore pairs of electrons to a metal ion. A “neutral donor ligand” is aneutrally charged ligand which donates one or more pairs of electrons toa metal ion.

A scavenger is a compound that is typically added to facilitateoligomerization or polymerization by scavenging impurities. Somescavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Inan embodiment of the invention a co-activator can be pre-mixed with thecatalyst compound to form an alkylated catalyst compound.

A propylene polymer is a polymer having at least 50 mol % of propylene.As used herein, Mn is number average molecular weight as determined byproton nuclear magnetic resonance spectroscopy (¹H NMR) unless statedotherwise, Mw is weight average molecular weight determined by gelpermeation chromatography (GPC), and Mz is z average molecular weightdetermined by GPC, wt % is weight percent, and mol % is mole percent.Molecular weight distribution (MWD) is defined to be Mw divided by Mn.Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz,are g/mol.

The following abbreviations may be used through this specification: Meis methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl,n-Pr is normal propyl, Bu is butyl, iso-butyl is isobutyl, sec-butylrefers to secondary butyl, tert-butyl, refers to tertiary butyl, n-butylis normal butyl, pMe is para-methyl, Bn is benzyl, THF istetrahydrofuran, Mes is mesityl, also known as 1,3,5-trimethylbenzene,Tol is toluene, TMS is trimethylsilyl, TIBAL is triisobutylaluminum,TNOAL is triisobutyl n-octylaluminum, MAO is methylalumoxane, MOMO ismethoxymethoxy (also referred to as methoxymethyl ether), N is nitrogen(including that N¹, N², N³ and N⁴ are nitrogen) and O is oxygen.

For purposes herein, RT is room temperature, which is defined as 25° C.unless otherwise specified. All percentages are weight percent (wt %)unless otherwise specified.

In the description herein, the Salan catalyst may be described as acatalyst precursor, a pre-catalyst compound, Salan catalyst compound ora transition metal compound, and these terms are used interchangeably.

Catalyst Compounds

In an embodiment of the invention, the catalyst comprises Group 3, 4, 5and/or 6 dialkyl compounds supported by a tetradentate di-anionic Salanligand, useful to polymerize olefins and/or α-olefins to producepolyolefins and/or poly(α-olefins).

In an embodiment of the invention, the catalyst compounds arerepresented by the formula:

-   -   wherein A and A′ are heteroaryl radicals subject to the proviso        that neither A nor A′ are substituted or unsubstituted        carbazolyl radicals;    -   M is a Group 3, 4, 5 or 6 transition metal;    -   N¹ and N² are nitrogen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁷, and R²⁸        is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a        functional group comprising elements from Group 13-17 of the        periodic table of the elements, or a combination thereof; and    -   Y and Z together form a divalent C₁ to C₂₀ hydrocarbyl radical,        preferably a C₂ to C₂₀ hydrocarbyl radical, preferably Y and Z        form a C₁-C₄₀ hydrocarbyl radical comprising a portion that        comprises a linker backbone comprising from 1 to 18 carbon atoms        linking the nitrogen atoms N¹ and N² wherein the hydrocarbyl        comprises 0, S, S(O), S(O)₂, Si(R*)₂, P(R*), N or N(R*), wherein        each R* is independently a C₁-C₁₈ hydrocarbyl, preferably in any        embodiment of the invention, Y—Z is selected from the group        consisting of ethylene (—CH₂CH₂—) and 1,2-cyclohexylene, and/or        —CH₂CH₂CH₂— derived from propylene. In an embodiment of the        invention, Y—Z is —CH₂CH₂CH₂— derived from propylene.

In an embodiment of the invention, the catalyst compounds arerepresented by the following structure:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to        each oxygen atom, and bonded with varying degrees of covalency        and coordination to each of nitrogen atoms N¹ and N²;    -   N³ and N⁴ are nitrogen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   Y is a divalent hydrocarbyl radical covalently bonded to and        bridging between both of the nitrogen atoms N¹ and N², subject        to the proviso that the diphenyl amine ligands attached to N³        and N⁴ are not directly bridged to each other to form a        carbazole moiety; and    -   each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen,        a C₁-C₄₀ hydrocarbyl radical, a functional group comprising        elements from Group 13-17 of the periodic table of the elements,        or two or more of R¹ to R³² may independently join together to        form a C₄ to C₆₂ cyclic or polycyclic ring structure wherein R⁶        and R²⁹ are not directly bridged to R¹³ or R³⁰ and wherein R²⁶        and R³¹ are not directly bridged to R¹⁹ or R³², or a combination        thereof.

In any embodiment of the invention, M is a Group 4 metal, or M is Hf, Tiand/or Zr, or M is Hf or Zr.

In any embodiment of the invention, each of X¹ and X² is independentlyselected from the group consisting of hydrocarbyl radicals having from 1to 20 carbon atoms, hydrides, amides, alkoxides having from 1 to 20carbon atoms, sulfides, phosphides, halides, amines, phosphines, ethers,and combinations thereof.

In any embodiment of the invention, X¹ and X² together form a part of afused ring or a ring system having from 4 to 62 carbon atoms.

In any embodiment of the invention, each of X¹ and X² is independentlyselected from the group consisting of halides, alkyl radicals havingfrom 1 to 7 carbon atoms, benzyl radicals, or a combination thereof. Inan embodiment of the invention, each X is, independently, a halogen or aC₁ to C₇ hydrocarbyl radical.

In any embodiment of the invention, Y is a divalent hydrocarbyl radicalcovalently bonded to and bridging between both of the nitrogen atoms N¹and N², subject to the proviso that the diphenyl amine ligands attachedto N³ and N⁴ are not directly bridged to each other to form a carbazolemoiety.

In any embodiment of the invention, Y is a divalent C₁-C₄₀ hydrocarbylradical comprising a portion that comprises a linker backbone comprisingfrom 1 to 18 carbon atoms linking or bridging between nitrogen atoms N¹and N². In an embodiment of the invention, Y is a C₁-C₄₀ hydrocarbylradical comprising a portion that comprises a linker backbone comprisingfrom 1 to 18 carbon atoms linking the nitrogen atoms N¹ and N² whereinthe hydrocarbyl comprises 0, S, S(O), S(O)₂, Si(R*)₂, P(R*), N or N(R*),wherein each R^(*) is independently a C₁-C₁₈ hydrocarbyl. In anembodiment of the invention, Y is selected from the group consisting ofethylene (—CH₂CH₂—) and 1,2-cyclohexylene, and/or —CH₂CH₂CH₂— derivedfrom propylene. In an embodiment of the invention, Y is —CH₂CH₂CH₂—derived from propylene.

Preferably, each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen, a C₁-C₄₀hydrocarbyl radical, a functional group comprising elements from Group13-17 of the periodic table of the elements, or two or more of R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸,R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³²may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure other than carbazole, or a combination thereof.

In an embodiment of the invention, M is Zr; X¹ and X² are benzylradicals; R¹ and R¹⁴ are methyl radicals; R² through R¹³ and R¹⁵ throughR³² are hydrogen; and Y is ethylene (—CH₂CH₂—).

In an embodiment of the invention, M is Zr; X¹ and X² are benzylradicals; R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals; R², R³, R⁵ throughR¹³, R¹⁵, R¹⁶ and R¹⁸ through R³² are hydrogen; and Y is ethylene(—CH₂CH₂—).

Preferably, each R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁷, and R²⁸ isindependently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of each R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁷,and R²⁸ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure, or a combination thereof; and each R⁶, R¹³,R²⁶, R³⁰, R³¹, and R³² is, independently, a hydrogen, a C₁-C₄₀hydrocarbyl radical, a functional group comprising elements from Group13-17 of the periodic table of the elements, or a combination thereof.

In an embodiment of the invention, each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²²,R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently,hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical, or a C₁ to C₁₀hydrocarbyl radical. In an embodiment of the invention, one or more ofR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶,R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰,R³¹, and R³² is a methyl radical, a fluoride, or a combination thereof,subject to the proviso that the diphenyl amine ligands attached to N³and N⁴ are not directly bridged to each other to form a carbazolemoiety.

In an embodiment of the invention, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁹, R³⁰, R³¹, and R³² areselected to provide steric bulk, also referred to as steric hindrance.In an embodiment of the invention, one or more of R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁹, R³⁰, R³¹,and R³² has a molecular volume of greater than 250 cubic Å, or greaterthan 300 cubic Å, or greater than 500 cubic Å. For purposes herein,molecular volume is used as an approximation of spatial steric bulk.Comparison of substituents with differing molecular volumes allows thesubstituent with the smaller molecular volume to be considered “lessbulky” in comparison to the substituent with the larger molecularvolume. Conversely, a substituent with a larger molecular volume may beconsidered “more bulky” than a substituent with a smaller molecularvolume.

In an embodiment of the invention, one or more of R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁹, R³⁰, R³¹,and R³² comprise C₁ to C₂₀, or C₄ to C₂₀ hydrocarbyl radicals; —SR³³,—NR³⁴ ₂, and —PR³⁵ ₂, where each R³³, R³⁴, or R³⁵ is independently a C₁to C₃₀ hydrocarbyl as defined above.

In an embodiment of the invention, one or more of R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁹, R³⁰, R³¹,and R³² are selected to prevent free rotation of the phenyl ringsattached to N³ or N⁴ relative to the adjoining phenyl ring attached tothe same nitrogen atom at 0° C., at 25° C., at 50° C., and/or at 100°C., as determined by NMR spectroscopy.

Accordingly, in an embodiment of the invention, the stereo chemistry ofthe polyolefins produced, in particular the stereochemistry of thepolypropylene produced may be controlled by selecting the substituentson the each of the two sets of phenyl amine rings, i.e., by selectingthe molecular size of one or more of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁹, R³⁰, R³¹, and R³².

In an embodiment of the invention, R⁶, R¹³, R¹⁹, R²⁶, R²⁹, R³⁰, R³¹, andR³² are selected from the group consisting of hydrogen, halogen, andC₁-C₁₀ hydrocarbyl. In an embodiment of the invention, any bridgebetween R⁶ or R²⁹ and R¹³ or R³⁰, or any bridge between R²⁶ or R³¹ andR¹⁹ or R³² comprises at least one additional atom from Group 13-17 ofthe periodic table of the elements (i.e., the carbon atoms in the phenylrings are not directly bonded). In embodiments of the invention, R²⁹ andR³⁰, and/or R³¹ and R³², respectively, join together to form divalentradicals bridging the two respective phenyl rings in the diphenylamine,wherein the divalent radical may be selected from C₁-C₄₀ hydrocarbylradicals and functional groups comprising elements from Group 13-17. Inan embodiment of the invention the bridges are nonconjugated to form adiphenylamino substituent that is nonconjugated and has a non-flatgeometry relative to carbazole. In embodiments of the invention, bridgesof specific lengths between the two aromatic rings may retain some ofthe rigidity of the carbazole system while still not being aromatic, andoverall may have a more predictable steric character relative tocarbazole, for example. Bridges such as methylene, ethylene and higheralkylenes and oxo may be mentioned, as well as, for example, bridgesformed as in the following diphenylamine derivatives 9,10-dihydroacridine, 10,11-dihydro-5H-dibenzo[b,f]azepine and 1 OH-phenoxazine:

In an embodiment of the invention, a catalyst compound is represented bythe formula:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   M is a Group 3, 4, 5 or 6 transition metal as described above;    -   N¹, N², N³ and N⁴ are nitrogen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   Y¹ is a divalent C₁ to C₂₀ hydrocarbyl radical corresponding to        Y as described above;    -   Y² and Y³ are independently a divalent C₁ to C₂₀ hydrocarbyl        radical, a divalent functional group comprising elements from        Group 13-16 of the periodic table of the elements, or a        combination thereof; and    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Group 13-17        of the periodic table of the elements, or two or more of R¹ to        R²⁸ may independently join together to form a C₄ to C₆₂ cyclic        or polycyclic ring structure.

In embodiments of the invention, Y² and Y³ are independently divalent C₁to C₁₀ hydrocarbyl radicals, oxo or a combination thereof. Inembodiments of the invention, Y² and Y³ are nonconjugated. Inembodiments of the invention, Y² and Y³ are independently methylene,ethylene, propylene, butylene, or oxo. In embodiments of the invention,Y² and Y³ are the same. In embodiments of the invention, Y² and Y³ aredifferent.

In an embodiment of the invention, two or more different catalystcompounds are present in the catalyst system used herein. In anembodiment of the invention, two or more different catalyst compoundsare present in the reaction zone where the process(es) described hereinoccur. When two transition metal compound based catalysts are used inone reactor as a mixed catalyst system, the two transition metalcompounds are chosen such that the two are compatible. Compatiblecatalysts are those catalysts having similar kinetics of termination andinsertion of monomer and comonomer(s) and/or do not detrimentallyinteract with each other. For purposes herein, the term “incompatiblecatalysts” refers to and means catalysts that satisfy one or more of thefollowing:

1) those catalysts that when present together reduce the activity of atleast one of the catalysts by greater than 50%;

2) those catalysts that under the same reactive conditions producepolymers such that one of the polymers has a molecular weight that ismore than twice the molecular weight of the other polymer; and

3) those catalysts that differ in comonomer incorporation or reactivityratio under the same conditions by more than about 30%. A simplescreening method such as by ¹H or ¹³C NMR, known to those of ordinaryskill in the art, can be used to determine which transition metalcompounds are compatible. In an embodiment of the invention, thecatalyst systems use the same activator for the catalyst compounds. Inan embodiment of the invention, two or more different activators, suchas a non-coordinating anion activator and an alumoxane, can be used incombination. If one or more catalyst compounds contain an X¹ or X²ligand which is not a hydride, or a hydrocarbyl, then in an embodimentof the invention the alumoxane is contacted with the catalyst compoundsprior to addition of the non-coordinating anion activator.

In an embodiment of the invention, when two transition metal compounds(pre-catalysts) are utilized, they may be used in any ratio. In anembodiment of the invention, a molar ratio of a first transition metalcompound (A) to a second transition metal compound (B) will fall withinthe range of (A:B) 1:1000 to 1000:1, or 1:100 to 500:1, or 1:10 to200:1, or 1:1 to 100:1, or 1:1 to 75:1, or 5:1 to 50:1. The particularratio chosen will depend on the exact pre-catalysts chosen, the methodof activation, and the end product desired. In an embodiment of theinvention, when using two pre-catalysts, where both are activated withthe same activator, useful mole percents, based upon the total moles ofthe pre-catalysts, are 10:90 to 0.1:99, or 25:75 to 99:1, or 50:50 to99.5:0.5, or 50:50 to 99:1, or 75:25 to 99:1, or 90:10 to 99:1.

Methods to Prepare the Catalyst Compounds.

In an embodiment of the invention, the transition metal compounds may beprepared by two general synthetic routes. In an embodiment of theinvention, the parent Salan ligands may be prepared by a one-stepMannich reaction from the parent phenol (reaction A) or by a two-stepimine-condensation alkylation procedure if an aldehyde located ortho toa hydroxy functional group (e.g., a substituted salicylaldehyde basestructure) is used (reaction B). The Salan ligand is then converted intothe metal di-substituted catalyst precursor by reaction with the metaltetra-substituted starting material to yield the finished complex. In anembodiment of the invention, the Salan ligand is then converted into themetal dibenzyl catalyst precursor by reaction with the metal tetra-arylstarting material, e.g., tetrabenzyl, to yield the finished complex(reaction C).

Activators

The terms “cocatalyst” and “activator” are used interchangeably todescribe activators and are defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active catalystcompound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts. Activators may includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment of the invention, alumoxane activators are utilized asan activator in the catalyst composition. Alumoxanes are generallyoligomeric compounds containing —Al(R¹)—O— sub-units, where R¹ is analkyl radical. Examples of alumoxanes include methylalumoxane (MAO),modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.Alkylalumoxanes and modified alkylalumoxanes are suitable as catalystactivators, particularly when the catalyst precursor compound comprisesan abstractable ligand which is an alkyl, halide, alkoxide or amide.Mixtures of different alumoxanes and modified alumoxanes may also beused. In an embodiment of the invention, visually clear methylalumoxanemay be used. A cloudy or gelled alumoxane can be filtered to produce aclear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)described in U.S. Pat. No. 5,041,584 and/or commercially available fromAkzo Chemicals, Inc. under the trade designation ModifiedMethylalumoxane type 3A.

When the activator is an alumoxane (modified or unmodified), the maximumamount of activator is typically a 5000-fold molar excess Al/M over thecatalyst compound (per metal catalytic site). The minimumactivator-to-catalyst-compound, which is determined according to molarconcentration of the transition metal M, is typically 1 mole aluminum orless to mole of transition metal M. In an embodiment of the invention,the activator comprises alumoxane and the alumoxane is present at aratio of 1 mole aluminum or more to mole of catalyst compound. In anembodiment of the invention, the minimum activator-to-catalyst-compoundmolar ratio is a 1:1 molar ratio. Other examples of Al:M ranges includefrom 1:1 to 500:1, or from 1:1 to 200:1, or from 1:1 to 100:1, or from1:1 to 50:1.

In an embodiment of the invention, little or no alumoxane (i.e., lessthan 0.001 wt %) is used in the polymerization processes describedherein. In an embodiment of the invention, alumoxane is present at 0.00mole %, or the alumoxane is present at a molar ratio of aluminum tocatalyst compound transition metal less than 500:1, or less than 300:1,or less than 100:1, or less than 1:1.

The term “non-coordinating anion” (NCA) refers to an anion which eitherdoes not coordinate to a cation, or which is only weakly coordinated toa cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible with the polymerization or catalyst system, stabilize thetransition metal cation in the sense of balancing its ionic charge at+1, and yet are sufficiently labile to permit displacement duringpolymerization.

In an embodiment of the invention, an ionizing or stoichiometricactivator may be used, which may be neutral or ionic, such as tri(n-butyl) ammonium boron metalloid precursor, polyhalogenatedheteroborane anions (WO 98/43983), boric acid (U.S. Pat. No. 5,942,459),or a combination thereof. In an embodiment of the invention, neutral orionic activators alone or in combination with alumoxane or modifiedalumoxane activators may be used.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups or radicals can be the same or differentand in an embodiment of the invention are each independently selectedfrom substituted or unsubstituted alkyls, alkenyls, alkyns, aryls,alkoxy, and halogens. In an embodiment of the invention, the threegroups are independently selected from halogen, mono or multicyclic(including halosubstituted) aryls, alkyls, and alkenyl compounds, andmixtures thereof; or independently selected from alkenyl radicals having1 to 20 carbon atoms, alkyl radicals having 1 to 20 carbon atoms, alkoxyradicals having 1 to 20 carbon atoms and aryl or substituted arylradicals having 3 to 20 carbon atoms. In an embodiment of the invention,the three substituent groups are alkyl radicals having 1 to 20 carbonatoms, phenyl, naphthyl, or mixtures thereof. In an embodiment of theinvention, the three groups are halogenated aryl groups, e.g.,fluorinated aryl groups. Preferably, the neutral stoichiometricactivator is tris perfluorophenyl boron or tris perfluoronaphthyl boron.

In an embodiment of the invention, ionic stoichiometric activatorcompounds may include an active proton, or some other cation associatedwith, but not coordinated to, or only loosely coordinated to theremaining ion of the ionizing compound. Suitable examples includecompounds and the like described in European publications EP 0 570 982A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A; EP 0277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741; 5,206,197;5,241,025; 5,384,299; 5,502,124; and WO 1996/04319; all of which areherein fully incorporated by reference.

In an embodiment of the invention compounds useful as an activatorcomprise a cation, which is, for example, a Bronsted acid capable ofdonating a proton, and a compatible non-coordinating anion which anionis relatively large (bulky), capable of stabilizing the active catalystspecies (the Group 4 cation, e.g.) which is formed when the twocompounds are combined and said anion will be sufficiently labile to bedisplaced by olefinic, diolefinic or acetylenically unsaturatedsubstrates or other neutral Lewis bases, such as ethers, amines, and thelike. Two classes of useful compatible non-coordinating anions aredisclosed in EP 0 277,003 A1, and EP 0 277,004 A1, which include anioniccoordination complexes comprising a plurality of lipophilic radicalscovalently coordinated to and shielding a central charge-bearing metalor metalloid core; and anions comprising a plurality of boron atoms suchas carboranes, metallacarboranes, and boranes.

In an embodiment of the invention, the stoichiometric activators includea cation and an anion component, and may be represented by the followingformula (1):

(Z)_(d) ⁺(A^(d−))  (1)

wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base;H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinatinganion having the charge d−; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe catalyst precursor, resulting in a cationic transition metalspecies, or the activating cation (L-H)_(d) ⁺ is a Bronsted acid,capable of donating a proton to the catalyst precursor resulting in atransition metal cation, including ammoniums, oxoniums, phosphoniums,silyliums, and mixtures thereof, or ammoniums of methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine,pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline,phosphoniums from triethylphosphine, triphenylphosphine, anddiphenylphosphine, oxoniums from ethers, such as dimethyl ether diethylether, tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid it may be represented by the formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, or a C₁to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In an embodiment of theinvention, the reducible Lewis acid is triphenyl carbenium.

Examples of the anion component A^(d−) include those having the formula[M^(k+)Q_(n)]d⁻ wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5 or 6, or 3,4, 5 or 6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, or boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl radicals, said Q having up to 20 carbon atoms with theproviso that in not more than one occurrence is Q a halide, and two Qgroups may form a ring structure. Each Q may be a fluorinatedhydrocarbyl radical having 1 to 20 carbon atoms, or each Q is afluorinated aryl radical, or each Q is a pentafluoryl aryl radical.Examples of suitable A^(d−) components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In an embodiment of the invention, this invention relates to a method topolymerize olefins comprising contacting olefins (e.g., ethylene) with aSalan catalyst compound, a chain transfer agent (CTA) and a boroncontaining NCA activator represented by the formula (1) where: Z is(L-H) or a reducible Lewis acid; L is a neutral Lewis base (as furtherdescribed above); H is hydrogen; (L-H) is a Bronsted acid (as furtherdescribed above); A^(d−) is a boron containing non-coordinating anionhaving the charged (as further described above); d is 1, 2, or 3.

In an embodiment of the invention in any of the NCA's represented byFormula 1 described above, the anion component A^(d−) is represented bythe formula [M*^(k)*⁺Q*_(n*)]^(d)*⁻ wherein k* is 1, 2, or 3; n* is 1,2, 3, 4, 5, or 6 (or 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* isindependently selected from hydride, bridged or unbridged dialkylamido,halogen, alkoxide, aryloxide, hydrocarbyl radicals, said Q* having up to20 carbon atoms with the proviso that in not more than 1 occurrence isQ* a halogen.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as ethylene) with a Salan catalyst compound asdescribed above, optionally with a CTA and an NCA activator representedby the Formula (2):

R_(n)M**(ArNHal)_(4-n)  (2)

where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, or the cation is Z_(d) ⁺ as described above.

In an embodiment of the invention in any of the NCA's comprising ananion represented by Formula 2 described above, R is selected from thegroup consisting of C₁ to C₃₀ hydrocarbyl radicals. In an embodiment ofthe invention, C₁ to C₃₀ hydrocarbyl radicals may be substituted withone or more C₁ to C₂₀ hydrocarbyl radicals, halide, hydrocarbylsubstituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido,arylsulfido, alkylphosphido, arylphosphide, or other anionicsubstituent; fluoride; bulky alkoxides, where bulky means C₄ to C₂₀hydrocarbyl radicals; —SR³³, —NR³⁴ ₂, and —PR³⁵ ₂, where each R³³, R³⁴,or R³⁵ is independently a C₁ to C₃₀ hydrocarbyl as defined above; or aC₁ to C₃₀ hydrocarbyl substituted organometalloid.

In an embodiment of the invention in any of the NCA's comprising ananion represented by Formula 2 described above, the NCA also comprisescation comprising a reducible Lewis acid represented by the formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, and/ora C₁ to C₄₀ hydrocarbyl, or the reducible Lewis acid represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with one ormore heteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment of the invention in any of the NCA's comprising ananion represented by Formula 2 described above, the NCA may alsocomprise a cation represented by the formula, (L-H)_(d) ⁺, wherein L isan neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is1, 2, or 3, or (L-H)_(d) ⁺ is a Bronsted acid selected from ammoniums,oxoniums, phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879, which are fully incorporated byreference herein.

In an embodiment of the invention, an activator useful herein comprisesa salt of a cationic oxidizing agent and a noncoordinating, compatibleanion represented by the Formula (3):

(OX^(e+))_(d)(A^(d−))_(e)  (3)

wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Suitable embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

In an embodiment of the invention, the Salan catalyst compounds, CTA's,and/or NCA's described herein can be used with bulky activators. A“bulky activator” as used herein refers to anionic activatorsrepresented by the formula:

-   wherein each R₁ is, independently, a halide, or a fluoride;-   each R₂ is, independently, a halide, a C₆ to C₂₀ substituted    aromatic hydrocarbyl radical or a siloxy group of the formula    —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or    hydrocarbylsilyl radical (or R₂ is a fluoride or a perfluorinated    phenyl radical);-   each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl    radical or a siloxy group of the formula —O—Si—R_(a), where R_(a) is    a C₁ to C₂₀ hydrocarbyl radical or hydrocarbylsilyl group (or R₃ is    a fluoride or a C₆ perfluorinated aromatic hydrocarbyl radical);    wherein R₂ and R₃ can form one or more saturated or unsaturated,    substituted or unsubstituted rings (or R₂ and R₃ form a    perfluorinated phenyl ring);-   L is an neutral Lewis base; (L-H)+ is a Bronsted acid; d is 1, 2, or    3;-   wherein the anion has a molecular weight of greater than 1020 g/mol;    and-   wherein at least three of the substituents on the B atom each have a    molecular volume of greater than 250 cubic Å, or greater than 300    cubic Å, or greater than 500 cubic Å.

As discussed above, “Molecular volume” is used herein as anapproximation of spatial steric bulk of an activator molecule insolution. Comparison of substituents with differing molecular volumesallows the substituent with the smaller molecular volume to beconsidered “less bulky” in comparison to the substituent with the largermolecular volume. Conversely, a substituent with a larger molecularvolume may be considered “more bulky” than a substituent with a smallermolecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3V_(S), where V_(S) is the scaledvolume. V_(S) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Molecular Formula of MV Total each Per subst. MV Activator Structure ofboron substituents substituent (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl)borate

C₁₀F₇ 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl)borate

C₁₂F₉ 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 515 2060

Exemplary bulky activators useful in catalyst systems herein include:

-   trimethylammonium tetrakis(perfluoronaphthyl)borate,-   triethylammonium tetrakis(perfluoronaphthyl)borate,-   tripropylammonium tetrakis(perfluoronaphthyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,-   tropillium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylphosphonium tetrakis(perfluoronaphthyl)borate,-   triethylsilylium tetrakis(perfluoronaphthyl)borate,-   benzene(diazonium)tetrakis(perfluoronaphthyl)borate,-   trimethylammonium tetrakis(perfluorobiphenyl)borate,-   triethylammonium tetrakis(perfluorobiphenyl)borate,-   tripropylammonium tetrakis(perfluorobiphenyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,-   tropillium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylphosphonium tetrakis(perfluorobiphenyl)borate,-   triethylsilylium tetrakis(perfluorobiphenyl)borate,-   benzene(diazonium)tetrakis(perfluorobiphenyl)borate,-   [4-tert-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the types disclosed in    U.S. Pat. No. 7,297,653, which is fully incorporated by reference    herein.

Illustrative, but not limiting, examples of boron compounds which may beused as an activator in the processes according to the instantdisclosure include:

-   trimethylammonium tetraphenylborate,-   triethylammonium tetraphenylborate,-   tripropylammonium tetraphenylborate,-   tri(n-butyl)ammonium tetraphenylborate,-   tri(tert-butyl)ammonium tetraphenylborate,-   N,N-dimethylanilinium tetraphenylborate,-   N,N-diethylanilinium tetraphenylborate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,-   tropillium tetraphenylborate,-   triphenylcarbenium tetraphenylborate,-   triphenylphosphonium tetraphenylborate,-   triethylsilylium tetraphenylborate,-   benzene(diazonium)tetraphenylborate,-   trimethylammonium tetrakis(pentafluorophenyl)borate,-   triethylammonium tetrakis(pentafluorophenyl)borate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,-   tropillium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   triethylsilylium tetrakis(pentafluorophenyl)borate,-   benzene(diazonium)tetrakis(pentafluorophenyl)borate,-   trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,-   dimethyl(tert-butyl)ammonium    tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   trimethylammonium tetrakis(perfluoronaphthyl)borate,-   triethylammonium tetrakis(perfluoronaphthyl)borate,-   tripropylammonium tetrakis(perfluoronaphthyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,-   tropillium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylphosphonium tetrakis(perfluoronaphthyl)borate,-   triethylsilylium tetrakis(perfluoronaphthyl)borate,-   benzene(diazonium)tetrakis(perfluoronaphthyl)borate,-   trimethylammonium tetrakis(perfluorobiphenyl)borate,-   triethylammonium tetrakis(perfluorobiphenyl)borate,-   tripropylammonium tetrakis(perfluorobiphenyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,-   tropillium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylphosphonium tetrakis(perfluorobiphenyl)borate,-   triethylsilylium tetrakis(perfluorobiphenyl)borate,-   benzene(diazonium)tetrakis(perfluorobiphenyl)borate,-   trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(tert-butyl)ammonium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethylanilinium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,    and dialkyl ammonium salts, such as:-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, and    dicyclohexylammonium tetrakis(pentafluorophenyl)borate; and    additional tri-substituted phosphonium salts, such as    tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, and    tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate.

Suitable activators include:

-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(perfluorophenyl)borate,-   [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄ ⁻];    1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;    and tetrakis(pentafluorophenyl)borate,-   4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an embodiment of the invention, the activator comprises a triarylcarbonium (such as triphenylcarbenium tetraphenylborate,

-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis (3,5-bis(trifluoromethyl)phenyl)borate).

In an embodiment of the invention, the activator comprises one or moreof

-   trialkylammonium tetrakis(pentafluorophenyl)borate,-   N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,-   trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   trialkylammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate,-   trialkylammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate,-   trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dialkylanilinium tetrakis    (3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,    (where alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or    tert-butyl).

In an embodiment of the invention, any of the activators describedherein may be mixed together before or after combination with thecatalyst compound and/or CTA and/or NCA, or before being mixed with thecatalyst compound and/or CTA, and/or NCA.

In an embodiment of the invention two NCA activators may be used in thepolymerization and the molar ratio of the first NCA activator to thesecond NCA activator can be any ratio. In an embodiment of theinvention, the molar ratio of the first NCA activator to the second NCAactivator is 0.01:1 to 10,000:1, or 0.1:1 to 1000:1, or 1:1 to 100:1.

In an embodiment of the invention, the NCA activator-to-catalyst ratiois a 1:1 molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to500:1 or 1:1 to 1000:1. In an embodiment of the invention, the NCAactivator-to-catalyst ratio is 0.5:1 to 10:1, or 1:1 to 5:1.

In an embodiment of the invention, the catalyst compounds can becombined with combinations of alumoxanes and NCA's (see for example,U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,453,410, EP 0 573 120 B1, WO94/07928, and WO 95/14044 which discuss the use of an alumoxane incombination with an ionizing activator, all of which are incorporated byreference herein).

Useful chain transfer agents are typically alkylalumoxanes, a compoundrepresented by the formula AlR₃, ZnR₂ (where each R is, independently, aC₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl butyl, pentyl,hexyl, octyl or an isomer thereof) or a combination thereof, such asdiethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum,trioctylaluminum, or a combination thereof.

Scavengers or Co-Activators

In an embodiment of the invention the catalyst system may furtherinclude scavengers and/or co-activators. Suitable aluminum alkyl ororganoaluminum compounds which may be utilized as scavengers orco-activators include, for example, trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike. Other oxophilic species such as diethyl zinc may be used.

Catalyst Supports

In an embodiment of the invention, the catalyst system may comprise aninert support material. In an embodiment of the invention, the supportmaterial comprises a porous support material, for example, talc, and/orinorganic oxides. Other suitable support materials include zeolites,clays, organoclays, or any other organic or inorganic support materialand the like, or mixtures thereof.

In an embodiment of the invention, the support material is an inorganicoxide in a finely divided form. Suitable inorganic oxide materials foruse in catalyst systems herein include Groups 2, 4, 13, and 14 metaloxides, such as silica, alumina, and mixtures thereof. Other inorganicoxides that may be employed either alone or in combination with thesilica, and/or alumina include magnesia, titania, zirconia,montmorillonite, phyllosilicate, and/or the like. Other suitable supportmaterials include finely divided functionalized polyolefins, such asfinely divided polyethylene.

In an embodiment of the invention, the support material may have asurface area in the range of from about 10 to about 700 m²/g, porevolume in the range of from about 0.1 to about 4.0 cc/g and averageparticle size in the range of from about 5 to about 500 μm, or thesurface area of the support material is in the range of from about 50 toabout 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g andaverage particle size of from about 10 to about 200 μm. In an embodimentof the invention, a majority portion of the surface area of the supportmaterial is in the range is from about 100 to about 400 m²/g, porevolume is from about 0.8 to about 3.0 cc/g and average particle size isfrom about 5 to about 100 μm. In an embodiment of the invention, theaverage pore size of the support material is in the range of from 10 to1000 Å, or 50 to about 500 Å, or 75 to about 350 Å. In an embodiment ofthe invention, the support material is a high surface area, amorphoussilica having a surface area greater than or equal to about 300 m²/g,and/or a pore volume of 1.65 cm³/gm. Suitable silicas are marketed underthe tradenames of Davison 952 or Davison 955 by the Davison ChemicalDivision of W.R. Grace and Company. In an embodiment of the inventionthe support may comprise Davison 948.

In an embodiment of the invention, the support material should beessentially dry, that is, essentially free of absorbed water. Drying ofthe support material can be effected by heating or calcining at about100° C. to about 1000° C., or at a temperature of at least about 400°C., or 500° C., or 600° C. When the support material is silica, it isheated to at least 200° C., or about 200° C. to about 850° C., or atleast 600° C. for a time of about 1 minute to about 100 hours, or fromabout 12 hours to about 72 hours, or from about 24 hours to about 60hours. In an embodiment of the invention, the calcined support materialmust have at least some reactive hydroxyl (OH) groups to producesupported catalyst systems according to the instant disclosure.

In an embodiment of the invention, the calcined support material iscontacted with at least one polymerization catalyst comprising at leastone catalyst compound and an activator. In an embodiment of theinvention, the support material, having reactive surface groups,typically hydroxyl groups, is slurried in a non-polar solvent and theresulting slurry is contacted with a solution of a catalyst compound andan activator. In an embodiment of the invention, the slurry of thesupport material is first contacted with the activator for a period oftime in the range of from about 0.5 hours to about 24 hours, or fromabout 2 hours to about 16 hours, or from about 4 hours to about 8 hours.The solution of the catalyst compound is then contacted with theisolated support/activator. In an embodiment of the invention, thesupported catalyst system is generated in situ. In alternate embodimentof the invention, the slurry of the support material is first contactedwith the catalyst compound for a period of time in the range of fromabout 0.5 hours to about 24 hours, or from about 2 hours to about 16hours, or from about 4 hours to about 8 hours. The slurry of thesupported catalyst compound is then contacted with the activatorsolution.

In an embodiment of the invention, the mixture of the catalyst,activator and support is heated to about 0° C. to about 70° C., or toabout 23° C. to about 60° C., or to room temperature. Contact timestypically range from about 0.5 hours to about 24 hours, or from about 2hours to about 16 hours, or from about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator and the catalyst compound are at leastpartially soluble and which are liquid at reaction temperatures.Suitable non-polar solvents include alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

Polymerization Processes

In an embodiment of the invention, a polymerization process includescontacting monomers (such as ethylene and propylene), and optionallycomonomers, with a catalyst system comprising an activator and at leastone catalyst compound, as described above. In an embodiment of theinvention, the catalyst compound and activator may be combined in anyorder, and may be combined prior to contacting with the monomer. In anembodiment of the invention, the catalyst compound and/or the activatorare combined after contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, or C₂ to C₂₀ alpha olefins, or C₂ to C₁₂ alpha olefins,or ethylene, propylene, butene, pentene, hexene, heptene, octene,nonene, decene, undecene, dodecene and isomers thereof. In an embodimentof the invention, the monomer comprises propylene and an optionalcomonomer(s) comprising one or more ethylene or C₄ to C₄₀ olefins, or C₄to C₂₀ olefins, or C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers maybe linear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups. In anembodiment of the invention, the monomer comprises ethylene or ethyleneand a comonomer comprising one or more C₃ to C₄₀ olefins, or C₄ to C₂₀olefins, or C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may belinear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, or hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, ornorbornene, norbornadiene, and dicyclopentadiene.

In an embodiment of the invention one or more dienes are present in thepolymer produced herein at up to 10 weight %, or at 0.00001 to 1.0weight %, or 0.002 to 0.5 weight %, or 0.003 to 0.2 weight %, based uponthe total weight of the composition. In an embodiment of the invention500 ppm or less of diene is added to the polymerization, or 400 ppm orless, or 300 ppm or less. In an embodiment of the invention at least 50ppm of diene is added to the polymerization, or 100 ppm or more, or 150ppm or more.

Diolefin monomers useful in this invention include any hydrocarbonstructure, or C₄ to C₃₀, having at least two unsaturated bonds, whereinat least two of the unsaturated bonds are readily incorporated into apolymer by either a stereospecific or a non-stereospecific catalyst(s).In an embodiment of the invention, the diolefin monomers may be selectedfrom alpha, omega-diene monomers (i.e. di-vinyl monomers). Preferably,the diolefin monomers are linear di-vinyl monomers, most or thosecontaining from 4 to 30 carbon atoms. Examples of dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and lowmolecular weight polybutadienes (Mw less than 1000 g/mol). Cyclic dienesinclude cyclopentadiene, vinylnorbornene, norbornadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene or higher ring containingdiolefins with or without substituents at various ring positions.

In an embodiment of the invention, where butene is the comonomer, thebutene source may be a mixed butene stream comprising various isomers ofbutene. The 1-butene monomers are expected to be preferentially consumedby the polymerization process. Use of such mixed butene streams willprovide an economic benefit, as these mixed streams are often wastestreams from refining processes, for example, C₄ raffinate streams, andcan therefore be substantially less expensive than pure 1-butene.

Polymerization processes according to the instant disclosure may becarried out in any manner known in the art. Any suspension, homogeneous,bulk, solution, slurry, or gas phase polymerization process known in theart can be used. Such processes can be run in a batch, semi-batch, orcontinuous mode. Homogeneous polymerization processes and slurryprocesses are suitable for use herein, wherein a homogeneouspolymerization process is defined to be a process where at least 90 wt %of the product is soluble in the reaction media. A bulk homogeneousprocess is suitable for use herein, wherein a bulk process is defined tobe a process where monomer concentration in all feeds to the reactor is70 volume % or more. In an embodiment of the invention, no solvent ordiluent is present or added in the reaction medium, (except for thesmall amounts used as the carrier for the catalyst system or otheradditives, or amounts typically found with the monomer; e.g., propane inpropylene). In an embodiment of the invention, the process is a slurryprocess. As used herein the term “slurry polymerization process” means apolymerization process where a supported catalyst is employed andmonomers are polymerized on the supported catalyst particles. At least95 wt % of polymer products derived from the supported catalyst are ingranular form as solid particles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene,and xylene. Suitable solvents also include liquid olefins which may actas monomers or comonomers including ethylene, propylene, 1-butene,1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene,1-decene, and mixtures thereof. In an embodiment of the invention,aliphatic hydrocarbon solvents are used as the solvent, such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In an embodiment of theinvention, the solvent is not aromatic, or aromatics are present in thesolvent at less than 1 wt %, or less than 0.5 wt %, or less than 0.0 wt% based upon the weight of the solvents.

In an embodiment of the invention, the feed concentration of themonomers and comonomers for the polymerization is 60 vol % solvent orless, or 40 vol % or less, or 20 vol % or less, based on the totalvolume of the feedstream. The polymerization may also be run in a bulkprocess.

Polymerizations can be run at any temperature and/or pressure suitableto obtain the desired ethylene polymers. Suitable temperatures and/orpressures include a temperature in the range of from about 0° C. toabout 300° C., or about 20° C. to about 200° C., or about 35° C. toabout 150° C., or from about 40° C. to about 120° C., or from about 45°C. to about 80° C.; and at a pressure in the range of from about 0.35MPa to about 10 MPa, or from about 0.45 MPa to about 6 MPa, or fromabout 0.5 MPa to about 4 MPa.

In an embodiment of the invention, the run time of the reaction is fromabout 0.1 minutes to about 24 hours, or up to 16 hours, or in the rangeof from about 5 to 250 minutes, or from about 10 to 120 minutes.

In an embodiment of the invention, hydrogen is present in thepolymerization reactor at a partial pressure of 0.001 to 50 psig (0.007to 345 kPa), or from 0.01 to 25 psig (0.07 to 172 kPa), or 0.1 to 10psig (0.7 to 70 kPa).

In an embodiment of the invention, the activity of the catalyst is atleast 50 g/mmol/hour, or 500 or more g/mmol/hour, or 5000 or moreg/mmol/hr, or 50,000 or more g/mmol/hr. In an alternate embodiment ofthe invention, the conversion of olefin monomer is at least 10%, basedupon polymer yield and the weight of the monomer entering the reactionzone, or 20% or more, or 30% or more, or 50% or more, or 80% or more.

In an embodiment of the invention, the polymerization conditions includeone or more of the following: 1) temperatures of 0 to 300° C. (or 25 to150° C., or 40 to 120° C., or 45 to 80° C.); 2) a pressure ofatmospheric pressure to 10 MPa (or 0.35 to 10 MPa, or from 0.45 to 6MPa, or from 0.5 to 4 MPa); 3) the presence of an aliphatic hydrocarbonsolvent (such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; or wherearomatics are or present in the solvent at less than 1 wt %, or lessthan 0.5 wt %, or at 0 wt % based upon the weight of the solvents); 4)wherein the catalyst system used in the polymerization comprises lessthan 0.5 mol %, or 0 mol % alumoxane, or the alumoxane is present at amolar ratio of aluminum to transition metal less than 500:1, or lessthan 300:1, or less than 100:1, or less than 1:1; 5) the polymerizationor occurs in one reaction zone; 6) the productivity of the catalystcompound is at least 80,000 g/mmol/hr (or at least 150,000 g/mmol/hr, orat least 200,000 g/mmol/hr, or at least 250,000 g/mmol/hr, or at least300,000 g/mmol/hr); 7) scavengers (such as trialkyl aluminum compounds)are absent (e.g., present at zero mol %) or the scavenger is present ata molar ratio of scavenger to transition metal of less than 100:1, orless than 50:1, or less than 15:1, or less than 10:1; and/or 8)optionally hydrogen is present in the polymerization reactor at apartial pressure of 0.007 to 345 kPa (0.001 to 50 psig) (or from 0.07 to172 kPa (0.01 to 25 psig), or 0.7 to 70 kPa (0.1 to 10 psig)).

In an embodiment of the invention, the catalyst system used in thepolymerization comprises no more than one catalyst compound. A “reactionzone” also referred to as a “polymerization zone” is a vessel wherepolymerization takes place, for example a batch reactor. When multiplereactors are used in either series or parallel configuration, eachreactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In an embodiment of the invention, thepolymerization occurs in one reaction zone.

Polyolefin Products

The instant disclosure also relates to compositions of matter producedby the methods described herein.

In an embodiment of the invention, the process described herein producespropylene homopolymers or propylene copolymers, such aspropylene-ethylene and/or propylene-α-olefin (or C₃ to C₂₀) copolymers(such as propylene-hexene copolymers or propylene-octene copolymers)having a Mw/Mn of greater than 1 to 4 (or greater than 1 to 3).

Likewise, the process of this invention produces olefin polymers, orpolyethylene and polypropylene homopolymers and copolymers. In anembodiment of the invention, the polymers produced herein arehomopolymers of ethylene or propylene, are copolymers of ethylene orhaving from 0 to 25 mole % (or from 0.5 to 20 mole %, or from 1 to 15mole %, or from 3 to 10 mole %) of one or more C₃ to C₂₀ olefincomonomer (or C₃ to C₁₂ alpha-olefin, or propylene, butene, hexene,octene, decene, dodecene, or propylene, butene, hexene, octene), or arecopolymers of propylene or having from 0 to 25 mole % (or from 0.5 to 20mole %, or from 1 to 15 mole %, or from 3 to 10 mole %) of one or moreof C₂ or C₄ to C₂₀ olefin comonomer (or ethylene or C₄ to C₁₂alpha-olefin, or ethylene, butene, hexene, octene, decene, dodecene, orethylene, butene, hexene, octene).

In an embodiment of the invention, the polymers produced herein have anMw of 5,000 to 1,000,000 g/mol (e.g., 25,000 to 750,000 g/mol, or 50,000to 500,000 g/mol), and/or an Mw/Mn of greater than 1 to 40, or 1.2 to20, or 1.3 to 10, or 1.4 to 5, or 1.5 to 4, or 1.5 to 3.

In an embodiment of the invention, the polymer produced herein has aunimodal or multimodal molecular weight distribution as determined byGel Permeation Chromatography (GPC). By “unimodal” is meant that the GPCtrace has one peak or inflection point. By “multimodal” is meant thatthe GPC trace has at least two peaks or inflection points. An inflectionpoint is that point where the second derivative of the curve changes insign (e.g., from negative to positive or vice versa).

Unless otherwise indicated Mw, Mn, MWD are determined by GPC asdescribed in US 2006/0173123 page 24-25, paragraphs [0334] to [0341].

In an embodiment of the invention, the instant catalyst is used toproduce vinyl terminated propylene polymers having unsaturated chain endor terminus. The unsaturated chain end of the vinyl terminatedmacromonomer comprises an “allyl chain end”, a vinylidene chain end, ora “3-alkyl” chain end.

An allyl chain end is represented by CH₂CH—CH²⁻, as shown in theformula:

where M represents the polymer chain. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup,” and “vinyl terminated” are used interchangeably in the followingdescription. The number of allyl chain ends, vinylidene chain ends,vinylene chain ends, and other unsaturated chain ends is determinedusing ¹H NMR at 120° C. using deuterated tetrachloroethane as thesolvent on an at least 250 MHz NMR spectrometer, and in selected cases,confirmed by ¹³C NMR. Resconi has reported proton and carbon assignments(neat perdeuterated tetrachloroethane used for proton spectra, while a50:50 mixture of normal and perdeuterated tetrachloroethane was used forcarbon spectra; all spectra were recorded at 100° C. on a BRUKERspectrometer operating at 500 MHz for proton and 125 MHz for carbon) forvinyl terminated oligomers in J. American Chemical Soc., 114, 1992, pp.1025-1032 that are useful herein. Allyl chain ends are reported as amolar percentage of the total number of moles of unsaturated groups(that is, the sum of allyl chain ends, vinylidene chain ends, vinylenechain ends, and the like).

A vinylidene chain end is represented by the formula:

-   -   where R can be H, alkyl, aryl aralkyl, or alkaryl.

A 3-alkyl chain end (where the alkyl is a C₁ to C₃₈ alkyl), alsoreferred to as a “3-alkyl vinyl end group” or a “3-alkyl vinyltermination”, is represented by the formula:

where “

” represents the polyolefin chain and Rb is a C₁ to C₃₈ alkyl group, ora C₁ to C₂₀ alkyl group, such as methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like. Theamount of 3-alkyl chain ends is determined using ¹³C NMR as set outbelow.

¹³C NMR data is collected at 120° C. at a frequency of at least 100 MHz,using a BRUKER 400 MHz NMR spectrometer. A 90 degree pulse, anacquisition time adjusted to give a digital resolution between 0.1 and0.12 Hz, at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating is employed during the entire acquisitionperiod. The spectra is acquired with time averaging to provide a signalto noise level adequate to measure the signals of interest. Samples aredissolved in tetrachloroethane-d₂ at concentrations between 10 wt % to15 wt % prior to being inserted into the spectrometer magnet. Prior todata analysis spectra are referenced by setting the chemical shift ofthe TCE solvent signal to 74.39 ppm. Chain ends for quantization wereidentified using the signals shown in the table below. N-butyl andn-propyl were not reported due to their low abundance (less than 5%)relative to the chain ends shown in the table below.

Chain End ¹³C NMR Chemical Shift P~i-Bu 23-5 to 25.5 and 25.8 to 26.3ppm E~i-Bu 39.5 to 40.2 ppm P~Vinyl 41.5 to 43 ppm E~Vinyl 33.9 to 34.4ppm

The “allyl chain end to vinylidene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylidene chain ends. The “allyl chain end to vinylidene chain endratio” is defined to be the ratio of the percentage of allyl chain endsto the percentage of vinylene chain ends. Vinyl terminated macromonomerstypically also have a saturated chain end. In polymerizations wherepropylene is present, the polymer chain may initiate growth in apropylene monomer, thereby generating an isobutyl chain end. An“isobutyl chain end” is defined to be an end or terminus of a polymer,represented as shown in the formula below:

where M represents the polymer chain. Isobutyl chain ends are determinedaccording to the procedure set out in WO 2009/155471. The “isobutylchain end to allylic vinyl group ratio” is defined to be the ratio ofthe percentage of isobutyl chain ends to the percentage of allyl chainends. The “isobutyl chain end to alpha bromo carbon ratio” is defined tobe the ratio of the percentage of isobutyl chain ends to the percentageof brominated chain ends (at about 34 ppm).

In an embodiment of the invention, the propylene polymer produced usingthe instant catalyst comprises at least 50% vinyl or unsaturated chainends. In an embodiment of the invention, at least 90%, or at least 95%,or at least 99% vinylidene chain ends.

In an embodiment of the invention, the polyolefins produced using theinstant catalyst may be isotactic, highly isotactic, syndiotactic, orhighly syndiotactic propylene polymer. As used herein, “isotactic” isdefined as having at least 10% isotactic pentads, preferably having atleast 40% isotactic pentads of methyl groups derived from propyleneaccording to analysis by ¹³C-NMR. As used herein, “highly isotactic” isdefined as having at least 60% isotactic pentads according to analysisby ¹³C-NMR. In a desirable embodiment, the vinyl terminated polyolefin(preferably polypropylene) has at least 85% isotacticity. As usedherein, “syndiotactic” is defined as having at least 10% syndiotacticpentads, preferably at least 40%, according to analysis by ¹³C-NMR. Asused herein, “highly syndiotactic” is defined as having at least 60%syndiotactic pentads according to analysis by ¹³C-NMR. In anotherembodiment, the vinyl terminated polyolefin (preferably polypropylene)has at least 85% syndiotacticity.

In an embodiment of the invention, the polymers may be linear incharacter, which may be determined by elution fractionation, whereinnon-linear polymers have a CDBI of less than 45%, whereas linearpolyethylene types refer to polyethylene having a CDBI of greater than50%, the CDBI being determined as described in WO93/03093 (U.S. Pat. No.5,206,075). In an embodiment of the invention the polymer producedherein has a composition distribution breadth index (CDBI) of 50% ormore, or 60% or more, or 70% or more. CDBI is a measure of thecomposition distribution of monomer within the polymer chains and ismeasured by the procedure described in PCT publication WO 93/03093,published Feb. 18, 1993, specifically columns 7 and 8 as well as in Wildet al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S.Pat. No. 5,008,204, including that fractions having a weight averagemolecular weight (Mw) below 15,000 are ignored when determining CDBI.

Polymers with an Mw/Mn of 4.5 or less may include a significant level oflong chain branching. The long chain branching is understood to be theresult of the incorporation of terminally unsaturated polymer chains(formed by the specific termination reaction mechanism encountered withsingle site catalysts) into other polymer chains in a manner analogousto monomer incorporation. The branches are hence believed to be linearin structure and may be present at a level where no peaks can bespecifically attributed to such long chain branches in the ¹³C NMRspectrum. In an embodiment of the invention, the polymers producedaccording to the instant disclosure comprise a significant amount oflong chain branching, defined as having a ratio of long chain branchingof at least 7 carbons per 1000 carbon atoms as determined according tothe ¹³C NMR spectrum of greater than 0.5. In an embodiment of theinvention, the ratio of long chain branching with branches having atleast 7 carbons, per 1000 carbon atoms as determined according to the¹³C NMR spectrum is greater than 1, or greater than 1.5, or greater than2.

In an embodiment of the invention, the polymers produced according tothe instant disclosure include a significant amount of vinyltermination, defined as a ratio of vinyl groups per molecule of greaterthan or equal to 0.2. In an embodiment of the invention, the polymersaccording to the instant disclosure comprise a ratio of vinyl groups permolecule of greater than or equal to 0.5, or 0.7, or 0.8, or 0.9, or0.95, when determined according to the description provided in the J.American Chemical Soc., 114,1992, pp. 1025-1032, or an equivalentthereof.

Blends

In an embodiment of the invention, the polymer (or the polyethylene orpolypropylene) produced herein is combined with one or more additionalpolymers prior to being formed into a film, molded part or otherarticle. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE,HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, cross linkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In an embodiment of the invention, the polymer (or the polyethylene orpolypropylene) is present in the above blends, at from 10 to 99 wt %,based upon the weight of the polymers in the blend, or 20 to 95 wt %, orat least 30 to 90 wt %, or at least 40 to 90 wt %, or at least 50 to 90wt %, or at least 60 to 90 wt %, or at least 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of theinvention with one or more polymers (as described above), by connectingreactors together in series to make reactor blends or by using more thanone catalyst in the same reactor to produce multiple species of polymer.The polymers can be mixed together prior to being put into the extruderor may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX1010 or IRGANOX 1076 available from Ciba-Geigy); phosphites (e.g.,IRGAFOS 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

In an embodiment of the invention, any of the foregoing polymers, suchas the foregoing polypropylenes or blends thereof, may be used in avariety of end-use applications.

Applications include, for example, mono- or multi-layer blown, extruded,and/or shrink films. These films may be formed by any number of wellknown extrusion or coextrusion techniques, such as a blown bubble filmprocessing technique, wherein the composition can be extruded in amolten state through an annular die and then expanded to form auni-axial or biaxial orientation melt prior to being cooled to form atubular, blown film, which can then be axially slit and unfolded to forma flat film. Films may be subsequently unoriented, uniaxially oriented,or biaxially oriented to the same or different extents. One or more ofthe layers of the film may be oriented in the transverse and/orlongitudinal directions to the same or different extents. The uniaxialorientation can be accomplished using typical cold drawing or hotdrawing methods. Biaxial orientation can be accomplished using tenterframe equipment or a double bubble processes and may occur before orafter the individual layers are brought together. For example, apolyethylene layer can be extrusion coated or laminated onto an orientedpolypropylene layer or the polyethylene and polypropylene can becoextruded together into a film then oriented. Likewise, orientedpolypropylene could be laminated to oriented polyethylene or orientedpolyethylene could be coated onto polypropylene then optionally thecombination could be oriented even further. Typically the films areoriented in the machine direction (MD) at a ratio of up to 15, orbetween 5 and 7, and in the transverse direction (TD) at a ratio of upto 15, or 7 to 9. However, In an embodiment of the invention the film isoriented to the same extent in both the MD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

In an embodiment of the invention, one or more layers may be modified bycorona treatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In an embodiment of the invention, one or bothof the surface layers is modified by corona treatment.

Molded Products

The compositions described herein (or polypropylene compositions) mayalso be used to prepare molded products in any molding process,including but not limited to, injection molding, gas-assisted injectionmolding, extrusion blow molding, injection blow molding, injectionstretch blow molding, compression molding, rotational molding, foammolding, thermoforming, sheet extrusion, and profile extrusion. Themolding processes are well known to those of ordinary skill in the art.

Further, the compositions described herein (or polypropylenecompositions) may be shaped into desirable end use articles by anysuitable means known in the art. Thermoforming, vacuum forming, blowmolding, rotational molding, slush molding, transfer molding, wet lay-upor contact molding, cast molding, cold forming matched-die molding,injection molding, spray techniques, profile coextrusion, orcombinations thereof are typically used methods.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. Typically, an extrudate film of the composition ofthis invention (and any other layers or materials) is placed on ashuttle rack to hold it during heating. The shuttle rack indexes intothe oven which pre-heats the film before forming. Once the film isheated, the shuttle rack indexes back to the forming tool. The film isthen vacuumed onto the forming tool to hold it in place and the formingtool is closed. The tool stays closed to cool the film and the tool isthen opened. The shaped laminate is then removed from the tool. Thethermoforming is accomplished by vacuum, positive air pressure,plug-assisted vacuum forming, or combinations and variations of these,once the sheet of material reaches thermoforming temperatures, typicallyof from 140° C. to 185° C. or higher. A pre-stretched bubble step isused, especially on large parts, to improve material distribution.

Blow molding is another suitable forming means for use with thecompositions of this invention, which includes injection blow molding,multi-layer blow molding, extrusion blow molding, and stretch blowmolding, and is especially suitable for substantially closed or hollowobjects, such as, for example, gas tanks and other fluid containers.Blow molding is described in more detail in, for example, CONCISEENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, pp. 90-92 (JacquelineI. Kroschwitz, ed., John Wiley & Sons 1990).

Likewise, molded articles may be fabricated by injecting molten polymerinto a mold that shapes and solidifies the molten polymer into desirablegeometry and thickness of molded articles. Sheets may be made either byextruding a substantially flat profile from a die, onto a chill roll, orby calendaring. Sheets are generally considered to have a thickness offrom 254 μm to 2540 μm (10 mils to 100 mils), although any given sheetmay be substantially thicker.

Non-Wovens and Fibers

The polyolefin compositions described above may also be used to preparenonwoven fabrics and fibers of this invention in any nonwoven fabric andfiber making process, including but not limited to, melt blowing,spunbonding, film aperturing, and staple fiber carding. A continuousfilament process may also be used. A spunbonding process may also beused. The spunbonding process is well known in the art. Generally itinvolves the extrusion of fibers through a spinneret. These fibers arethen drawn using high velocity air and laid on an endless belt. Acalendar roll is generally then used to heat the web and bond the fibersto one another although other techniques may be used such as sonicbonding and adhesive bonding.

Embodiments Listing

Accordingly, the instant disclosure relates to the followingembodiments:

-   A. A catalyst compound represented by the formula:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², N³ and N⁴ are nitrogen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   Y is a divalent hydrocarbyl radical covalently bonded to and        bridging between both of the nitrogen atoms N¹ and N²; and each        R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,        R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,        R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen, a        C₁-C₄₀ hydrocarbyl radical, a functional group comprising        elements from Group 13-17 of the periodic table of the elements,        or two or more of R¹ to R³² may independently join together to        form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a        combination thereof.

-   B. The catalyst compound of embodiment A wherein M is Hf, Ti, or Zr.

-   C. The catalyst compound of embodiment A or embodiment B wherein    each X is, independently, a halogen or a C₁ to C₇ hydrocarbyl    radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,    benzyl, heptyl, chloro, benzo, iodo, and the like.

-   D. The catalyst compound of any one of embodiments A to C wherein    each X is a benzyl radical.

-   E. The catalyst compound of any one of embodiments A to D wherein Y    is —CH₂CH₂— or 1,2-cyclohexylene.

-   F. The catalyst compound of any one of embodiments A to E wherein Y    is —CH₂CH₂CH₂—.

-   G. The catalyst compound of any one of embodiments A to F wherein Y    is a C₁-C₄₀ divalent hydrocarbyl radical comprising a linker    backbone comprising from 1 to 18 carbon atoms bridging between    nitrogen atoms N¹ and N².

-   H. The catalyst compound of any one of embodiments A to G wherein Y    is a C₁-C₄₀ divalent hydrocarbyl radical comprising O, S, S(O),    S(O)₂, Si(R′)₂, P(R′), N, N(R′), or a combination thereof, wherein    each R′ is independently a C₁-C₁₈ hydrocarbyl radical.

-   I. The catalyst compound of any one of embodiments A to H wherein    each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,    R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen, a C₁-C₄₀    hydrocarbyl radical, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R³² may independently join together to form a C₄ to C₆₂ cyclic    or polycyclic ring structure wherein R⁶ and R²⁹ are not directly    bridged to R¹³ or R³⁰ and wherein R²⁶ and R³¹ are not directly    bridged to R¹⁹ or R³², or a combination thereof.

-   J. The catalyst compound of any one of embodiments A to I wherein    each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,    R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, a hydrogen, a C₁-C₄₀    hydrocarbyl radical, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R³² may independently join together to form a C₄ to C₆₂ cyclic    or polycyclic ring structure wherein neither R⁶ nor R²⁹ join    together with R¹³ or R³⁰ to form direct covalent bonds between the    respective aromatic rings and wherein neither R²⁶ n R³¹ join    together with R¹⁹ or R³² to form direct covalent bonds between the    respective aromatic rings.

-   K. The catalyst compound of any one of embodiments A to J wherein    each R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R¹⁵, R¹⁶,    R¹⁷, R¹⁸, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁷, and R²⁸ is    independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a    functional group comprising elements from Group 13-17 of the    periodic table of the elements, or two or more of R¹, R², R³, R⁴,    R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁰, R²¹,    R²², R²³, R²⁴, R²⁵, R²⁷ and R²⁸ may independently join together to    form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a    combination thereof; and each R⁶, R¹³, R¹⁹, R²⁶, R²⁹, R³⁰, R³¹ and    R³² is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a    functional group comprising elements from Group 13-17 of the    periodic table of the elements, or a combination thereof.

-   L. The catalyst compound of any one of embodiments A to K wherein    each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,    R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, hydrogen, a halogen,    or a C₁ to C₃₀ hydrocarbyl radical.

-   M. The catalyst compound of any one of embodiments A to L wherein    each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,    R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently, hydrogen, a halogen,    or a C₁ to C₁₀ hydrocarbyl radical.

-   N. The catalyst compound of any one of embodiments A to M, wherein    one or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,    R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵,    R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is a methyl radical, a    fluoride, or a combination thereof

-   O. The catalyst compound of any one of embodiments A to N wherein:    -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹ and R¹⁴ are methyl radicals;    -   R² through R¹³ and R¹⁵ through R³² are hydrogen; and    -   Y is —CH₂CH₂—.

-   P. The catalyst compound of any one of embodiments A to 0 wherein:    -   M is Zr;    -   X¹ and X² are benzyl radicals;    -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;    -   R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, and R¹⁸ through R³² are        hydrogen; and    -   Y is —CH₂CH₂—.

-   Q. The catalyst compound of any one of embodiments A to J wherein    R²⁹ and R³⁰ join together to form a divalent C₁ to C₂₀ hydrocarbyl    radical, a divalent functional group comprising elements from Group    13-16 of the periodic table of the elements, or a combination    thereof.

-   R. The catalyst compound of any one of embodiments A to J and Q    wherein R³¹ and R³² join together to form a divalent C₁ to C₂₀    hydrocarbyl radical, a divalent functional group comprising elements    from Group 13-16 of the periodic table of the elements, or a    combination thereof.

-   S. The catalyst compound of any one of embodiments A to J and Q to R    wherein the catalyst compound is represented by the formula:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   Y¹ is Y (a divalent C₁ to C₂₀ hydrocarbyl radical);    -   Y² and Y³ are independently a divalent C₁ to C₂₀ hydrocarbyl        radical, a divalent functional group comprising elements from        Group 13-16 of the periodic table of the elements, or a        combination thereof; and    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Group 13-17        of the periodic table of the elements, or two or more of R¹ to        R²⁸ may independently join together to form a C₄ to C₆₂ cyclic        or polycyclic ring structure.

-   T. The catalyst compound according to embodiment S wherein Y² and Y³    are independently divalent C₁ to C₁₀ hydrocarbyl radicals, oxo or a    combination thereof.

-   U. The catalyst compound according to embodiment S or embodiment T    wherein Y² and Y³ are methylene, ethylene, propylene, butylene, or    oxo.

-   V. The catalyst compound of any one of embodiments S to U wherein Y²    and Y³ are nonconjugated.

-   W. A catalyst system comprising an activator and the catalyst    compound of any one of embodiments A to V.

-   X. The catalyst system of embodiment W, wherein the activator    comprises alumoxane, a non-coordinating anion activator, or a    combination thereof.

-   Y. The catalyst system of embodiment W or embodiment X, wherein the    activator comprises alumoxane and the alumoxane is present at a    ratio of 1 mole aluminum or more to mole of catalyst compound.

-   Z. The catalyst system of any one of embodiments W to Y, wherein the    activator is represented by the formula:

(Z)d+(Ad−)

-   -   wherein Z is (L-H), or a reducible Lewis Acid, wherein L is a        neutral Lewis base;    -   H is hydrogen;    -   (L-H)+ is a Bronsted acid;    -   Ad− is a non-coordinating anion having the charge d−; and    -   d is an integer from 1 to 3.

-   A1. The catalyst system of any one of embodiments W to Z wherein the    activator is represented by the formula:

(Z)_(d)+(A^(d−))

-   -   wherein A^(d−) is a non-coordinating anion having the charge d⁻;    -   d is an integer from 1 to 3, and    -   Z is a reducible Lewis acid represented by the formula: (Ar₃C+),        where Ar is aryl radical, an aryl radical substituted with a        heteroatom, an aryl radical substituted with one or more C₁ to        C₄₀ hydrocarbyl radicals, an aryl radical substituted with one        or more functional groups comprising elements from Groups 13-17        of the periodic table of the elements, or a combination thereof

-   B1. A process to polymerize olefins comprising contacting one or    more olefins with the catalyst system of any one of embodiments W to    A1 at a temperature, a pressure, and for a period of time sufficient    to produce a polyolefin.

-   C1. The process of embodiment B1 wherein the conditions comprise a    temperature of from about 0° C. to about 300° C., a pressure from    about 0.35 MPa to about 10 MPa, and a time from about 0.1 minutes to    about 24 hours.

-   D1. The process of embodiment B1 or embodiment C1, wherein the one    or more olefins comprise propylene.

-   E1. The process of any one of embodiments B1 to D1 wherein the    polyolefin comprises at least 50 mole % propylene.

EXAMPLES

The foregoing discussion can be further described with reference to thefollowing non-limiting examples. Thirteen illustrative catalystcompounds (A through M), each according to one or more embodimentsdescribed, were synthesized and used to polymerize olefins. Allreactions were carried out under a purified nitrogen atmosphere usingstandard glovebox, high vacuum or Schlenk techniques, unless otherwisenoted. All solvents used were anhydrous, de-oxygenated and purifiedaccording to known procedures. All starting materials were eitherpurchased from Aldrich and purified prior to use or prepared accordingto procedures known to those skilled in the art. Comparative catalystcompound Cl was synthesized as described in WO 03/091292A2.

Synthesis of Compounds A-M:

Synthesis of 2: In a 100 mL round bottom flask, 1 (0.566 g, 2.056 mmol),N,N′-dimethylethylene diamine (0.111 g, 1.259 mmol), andparaformaldehyde (0.309 g, 10.290 mmol) were slurried in 30 mL ofethanol. The flask was then placed in an oil bath. The reaction wasstirred and heated to reflux overnight, during which all reactantsdissolved. Solvent was removed under a N₂ stream while heating leavingan orange oily residue. Residue was purified using a Biotage silicacolumn with a dual solvent system—Run A: 20-100% CH₂Cl₂/hexanes; Run B:5% MeOH/CH₂Cl₂. NMR of the fraction from Biotage run A shows thepresence of 1. The fraction from Biotage run B shows pure 2. Yield of 2was 0.331 g.

Synthesis of 3: In a nitrogen purged drybox, 2 and tetrabenzylzirconiumwere weighed out into separate vials and either slurried or dissolved in5 mL of toluene. The solution of ZrBn4 was then slowly added to thestirring slurry of 2. The reaction was left to stir for 3 hours. Themixture was filtered through an Acro-disc (0.2 micron) into anothervial. The volatiles were removed under N₂ stream. The resulting residuewas slurried in pentane for 20 minutes. The slurry was filtered througha fit and the solids washed with pentane. The solids were then driedunder vacuum. NMR of the dried solids shows pure 3. Yield of 3 was 0.166g.

Example 1

A PARR bomb equipped with a glass bottle was chilled to −85° C. To thiswas added MAO(s) (361.1 mg, 6.225 mmol) and 3 (11.9 mg, 0.0127 mmol).Propylene (1) (24.4 g, 580 mmol) was poured into the bottle. The PARRbomb was sealed over the bottle and heated to 70° C. for 1 hr. Thereactor was vented. The product was washed out of the PARR bomb withtoluene. The toluene was blown down under N₂ overnight. Collected 4.860g of a greenish liquid. Activity: 382 g polymer/(mmol Catalyst*hr) NMR:(C₆D₆): δ 0.9-1.8 (mn, 168.38H), 4.79 (d, 2.00H). 100% vinylidene, Mn1179 g/mol

Example 2

In a 20 mL vial 3 (9.1 mg, 0.0097 mmol) and (C₆H₅)₃C⁺B(C₆F₅)₄ ⁻ (9.2 mg,0.010 mmol) were combined together in ˜2 mL of toluene for 30 min. APARR bomb equipped with a glass bottle was chilled to −85° C.Tri-n-octyl aluminum (71 mg, 0.19 mmol) was added to the bottle followedby propylene (1) (24.5 g, 582 mmol). The catalyst solution was thenadded to the glass bottle and the PARR bomb was sealed over the bottleand heated to 70° C. for 1 hr. The reactor was vented. The product waswashed out of the PARR bomb with toluene. The toluene was blown downunder N2 overnight. Collected 7.880 g of a greenish liquid. Activity:809 g polymer/(mmol Catalyst*hr) NMR: (C₆D₆): δ 0.9-1.8 (mn, 226.47H),4.78 (d, 2.00H) 100% vinylidene, Mn=1585 g/mol

Example 3

A PARR bomb equipped with a glass bottle was chilled to −85° C. To thiswas added MAO(s) (348.0 mg, 5.999 mmol) and 3 (10.3 mg, 0.0110 mmol).Propylene (1) (25.0 g, 594 mmol) was poured into the bottle. The PARRbomb was sealed over the bottle and allowed to warm up to RT and stirovernight. The reactor was vented. The product was washed out of thePARR bomb with toluene. The toluene was blown down under N₂. Collected7.785 g of a greenish liquid. Activity: 706 g polymer/(mmol Catalyst*hr)NMR: NMR: (C₆D₆): δ 0.9-1.8 (mn, 155.55H), 4.78 (d, 2.00H) 100%vinylidene, Mn 1089 g/mol. The data are shown in Table 1.

TABLE 1 Yield Propylene Temp. ° C. Mn Rxn Time (hr) (g) Conversion (%)Example 1 70 1179 1 4.86 19.9 Example 2 70 1585 1 7.88 32.2 Example 3 201089 16 7.78 31.0

As the data show, the catalyst compounds, catalyst systems, andpolymerization processes disclosed herein provide novel and improvedcatalyst and systems for the polymerization of olefins, which producepolymers having improved properties, such as high polymer melting point,high polymer molecular weights, an increased conversion and/or comonomerincorporation, which may further include a significant amount of longchain branching and/or a significant amount of vinyl termination.

The catalysts in an embodiment of the invention provide improvement incatalyst activity, produce polymers with improved properties or both.Crystallographic techniques indicate that the appended ring system orsystems are oriented transversely, e.g., perpendicular, to the phenolrings. These catalysts have a structure to provide a broad corridor forthe polymeryl moiety to reside and for the monomer to insert during thepolymerization process. As such, catalysts according to one embodimentof the instant disclosure provide for an ability to control one or morecharacteristics of polymerization, tacticity, comonomer insertion, andthe like.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is NOT incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments of theinvention, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law. Likewise whenever a composition, an element or a groupof elements is preceded with the transitional phrase “comprising”, it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of”, “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A catalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; M is a Group 3, 4, 5 or 6 transition metal; N¹,N², N³ and N⁴ are nitrogen; each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure, provided however when M is trivalent X² is not present; Y isa divalent hydrocarbyl radical covalently bonded to and bridging betweenboth of the nitrogen atoms N¹ and N²; and each R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹,R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R³² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure wherein neither R⁶nor R²⁹ join together with R¹³ or R³⁰ to form direct covalent bondsbetween the respective aromatic rings and wherein neither R²⁶ nor R³¹join together with R¹⁹ or R³² to form direct covalent bonds between therespective aromatic, or a combination thereof.
 2. The catalyst compoundof claim 1 wherein M is Hf, Ti, or Zr.
 3. The catalyst compound of claim1 wherein each X is, independently, a halogen or a C₁ to C₇ hydrocarbylradical.
 4. The catalyst compound of claim 1 wherein each X is a benzylradical.
 5. The catalyst compound of claim 1 wherein Y is —CH₂CH₂— or1,2-cyclohexylene.
 6. The catalyst compound of claim 1 wherein Y is—CH₂CH₂CH₂—.
 7. The catalyst compound of claim 1 wherein Y is a C₁-C₄₀divalent hydrocarbyl radical comprising a linker backbone comprisingfrom 1 to 18 carbon atoms bridging between nitrogen atoms N¹ and N². 8.The catalyst compound of claim 1, wherein Y is a C₁-C₄₀ divalenthydrocarbyl radical comprising O, S, S(O), S(O)₂, Si(R′)₂, P(R′), N,N(R′), or a combination thereof, wherein each R′ is independently aC₁-C₁₈ hydrocarbyl radical.
 9. The catalyst compound of claim 1 whereineach R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁷ and R²⁸ is, independently, ahydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group comprisingelements from Group 13-17 of the periodic table of the elements, or twoor more of R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R¹⁵, R¹⁶,R¹⁷, R¹⁸, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁷ and R²⁸ may independentlyjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure,or a combination thereof and each R⁶, R¹³, R¹⁹, R²⁶, R²⁹, R³⁰, R³¹ andR³² is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, afunctional group comprising elements from Group 13-17 of the periodictable of the elements, or a combination thereof.
 10. The catalystcompound of claim 1 wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently,hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical.
 11. Thecatalyst compound of claim 1 wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²²,R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is, independently,hydrogen, a halogen, or a C₁ to C₁₀ hydrocarbyl radical.
 12. Thecatalyst compound of claim 1 wherein one or more of R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰,R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is amethyl radical, a fluoride, or a combination thereof.
 13. The catalystcompound of claim 1, wherein R²⁹ and R³⁰ join together to form adivalent C₁ to C₂₀ hydrocarbyl radical, a divalent functional groupcomprising elements from Group 13-16 of the periodic table of theelements, or a combination thereof, and wherein R³¹ and R³² jointogether to form a divalent C₁ to C₂₀ hydrocarbyl radical, a divalentfunctional group comprising elements from Group 13-16 of the periodictable of the elements, or a combination thereof.
 14. The catalystcompound of claim 1 wherein: M is Zr; X¹ and X² are benzyl radicals; R¹and R¹⁴ are methyl radicals; R² through R¹³ and R¹⁵ through R³² arehydrogen; and Y is —CH₂CH₂—.
 15. The catalyst compound of claim 1wherein: M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴ and R¹⁷ aremethyl radicals; R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, and R¹⁸ through R³²are hydrogen; and Y is —CH₂CH₂—.
 16. A catalyst compound represented bythe formula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; M is a Group 3, 4, 5 or 6 transition metal; N¹,N², N³ and N⁴ are nitrogen; each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure, provided however when M is trivalent X² is not present; Y¹ isa divalent C₁ to C₂₀ hydrocarbyl radical; Y² and Y³ are independently adivalent C₁ to C₂₀ hydrocarbyl radical, a divalent functional groupcomprising elements from Group 13-16 of the periodic table of theelements, or a combination thereof; and each R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²²,R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀hydrocarbyl radical, a functional group comprising elements from Group13-17 of the periodic table of the elements, or two or more of R¹ to R²⁸may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure.
 17. A catalyst system comprising: an activator and acatalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; M is a Group 3, 4, 5 or 6 transition metal; N¹,N², N³ and N⁴ are nitrogen; each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure, provided however when M is trivalent X² is not present; Y isa divalent hydrocarbyl radical covalently bonded to and bridging betweenboth of the nitrogen atoms N¹ and N²; and each R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹,R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R³² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure wherein neither R⁶nor R²⁹ join together with R¹³ or R³⁰ to form direct covalent bondsbetween the respective aromatic rings and wherein neither R²⁶ nor R³¹join together with R¹⁹ or R³² to form direct covalent bonds between therespective aromatic rings, or a combination thereof.
 18. The catalystsystem of claim 17, wherein the activator comprises alumoxane, anon-coordinating anion activator, or a combination thereof.
 19. Thecatalyst system of claim 17, wherein the activator comprises alumoxaneand the alumoxane is present at a ratio of 1 mole aluminum or more tomole of catalyst compound.
 20. The catalyst system of claim 17, whereinthe activator is represented by the formula:(Z)_(d) ⁺(A^(d−)) wherein Z is (L-H), or a reducible Lewis Acid, whereinL is a neutral Lewis base; H is hydrogen; (L-H)+ is a Bronsted acid;A^(d−) is a non-coordinating anion having the charge d⁻; and d is aninteger from 1 to
 3. 21. The catalyst system of claim 17 wherein theactivator is represented by the formula:(Z)_(d)+(A^(d−)) wherein A^(d−) is a non-coordinating anion having thecharge d⁻; d is an integer from 1 to 3, and Z is a reducible Lewis acidrepresented by the formula: (Ar₃C⁺), where Ar is aryl radical, an arylradical substituted with a heteroatom, an aryl radical substituted withone or more C₁ to C₄₀ hydrocarbyl radicals, an aryl radical substitutedwith one or more functional groups comprising elements from Groups 13-17of the periodic table of the elements, or a combination thereof.
 22. Aprocess to polymerize olefins comprising: contacting one or more olefinswith a catalyst system at a temperature, a pressure, and for a period oftime sufficient to produce a polyolefin, the catalyst system comprisingan activator and a catalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; M is a Group 3, 4, 5 or 6 transition metal; N¹,N², N³ and N⁴ are nitrogen; each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure, provided however when M is trivalent X² is not present; Y isa divalent hydrocarbyl radical covalently bonded to and bridging betweenboth of the nitrogen atoms N¹ and N²; and each R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹,R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, and R³² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R³² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure wherein neither R⁶nor R²⁹ join together with R¹³ or R³⁰ to form direct covalent bondsbetween the respective aromatic rings and wherein neither R²⁶ nor R³¹join together with R¹⁹ or R³² to form direct covalent bonds between therespective aromatic rings, or a combination thereof.
 23. The process ofclaim 22, wherein the one or more olefins comprise propylene.
 24. Theprocess of claim 22 wherein the polyolefin comprises at least 50 mole %propylene.